Underwater laser machining process is an alternative method to cut materials with less thermal damage due to the water cooling of workpiece during the ablation. However, the rapid cooling induced by water can instantly solidify the laser-molten material rather than expel it to form a cut. To understand the roles of processing temperature on ablation performance in water, this paper presents the influences of water temperature on cut width, depth, and surface morphology in the underwater laser grooving of silicon. The effects of laser power, laser traverse speed, and number of laser passes on the groove characteristics were also examined in this work. The results revealed that using high water temperature can increase the groove aspect ratio, particularly when high laser power, slow traverse speed, and multiple laser passes were employed. However, debris deposition and oxides were found on the laser-ablated surface when processing at high water temperature. The implication of this study could enhance the ablation rate for the underwater laser as well as low-power laser cutting systems.